Photographic color development process



Dec. 23, 1958 P. M. MADER 2,855,747

PHOTOGRAPHIC COLOR DEVELOPMENT PROCESS Filed Dec. 22, 1955 EXPOSURE S/L VEI? HAL/DE- COUPLE/i HYDROOU/IVO/VE DER/I44 T VE AM/A/OPHEA/OL 0/? v PY/PAZOL/DO/VE DEVELOPMENT Sfage 2 mac/1 AND F/)( 0u//v0/v0/0 IMAGE Stage 3 J COLOR DEVELOPMENT /2 4 :\\.Q:,A.s\\\

PA UL M. MADE/P IN VEN TOR.

BY M UW ATTORNEY 8 AGE/VT compounds.

PHOTOGRAPHIC COLOR DEVELOPMENT PROCESS Paul M. Mader, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application December 22, 1955, Serial N0. 554,8270 I 6Claims. or. 96-55) I This invention relates to a photographic color reproduction process involving the use of coupler compounds and color developing agents which 'is distinct from conventional color processes employing color development in that the dye image formation is carried out at a stage-in the process at which no silver halide is present.

That is, in conventional processes of color photography employing color development, exposed silver halide emulsion layers are developed with a primary aromatic amino silver halide developing agent in the presence of a coupler compound such as the naphthol and pyrazolone coupler During the color development step the coupler compound reacts with the oxidation product ofthe developing agent to form a dye image in situ with the developed silver. Thereafter the silver image and residual silver halide are removed from the emulsion layer by well-known silver bleaching and fixing operations.

My process involves the use of silver halide emulsion layers containing a mixture of any of the well-known types of coupler compounds and'of -a non-diffusing or slowly diifusing hydroquinone derivative capable of being oxidized by the oxidized forms of high energy silver halide developers.

tially water-insoluble organic crystalloidal coupler solvent such as dibutylphthalate, and this solution is dispersed in the emulsion layer. After exposure, the emulsion layer is developed in a black-and-white developer containing as an active developing agent a substance the oxidized form of which is capable of oxidizing the hydroquinone derivative incorporated in the emulsion layer. Under these conditions, the oxidized developer formed in regions of silver development in turn oxidizes the incorpo'rated hydroquinone derivative, giving a quinonoid image in situ with the silver image. Thereafter the emulsion layer is bleached and fixed to remove silver and residual silver halide, leaving the quinonoid image in the layer together with the coupler compound. Subsequent treat: ment of the layer in an alkaline solution of a color de veloping agent causes production of a dye image in the region of the original silver image. This dye is formed through reactions involving the color developing agent, the quinonoid substance in the image, and the coupler.

One advantageous feature of my process as compared to ordinary color development processes will be apparent. Since the bleaching and fixing operations are carried out prior to the color development step, it is possible to obtain color reproductions which have appreciably less stain in the highlight regions. In the usual color develop rnent processes, the removal of the silver and residual 'silver halide by bleaching and fixing solutions is carried out subsequent to color development, and any color developer remaining in the emulsion layer is usually oxidized by the bleaching solution to form undesirable.stain.- The process of my invention will now be described with particular reference to the accompanying drawi-ng.

The coupler and hydroquinone derivative are dissolved together in a low molecular weight substan- Q The above solutions had the 2 EXAMPLE To a sample of a gelatino-bromoiodide emulsion containing 0.0085 mo] of silver halide was added a dispersion of the following ingredients:

Coupler. gm-.. 0.5 Sec.-octadecylhydroquinone gm 1.5 Dibutylphthalate 3 Gelatin (10%.aqueous solution) cc 18 Sodium triisopropyl naphthalene sulfonate (5% aqueous solution) c 3 Saponin solution (0.75% aqueous) 'cc 14 The emulsion thus prepared was then coated on a film 1. Black-and-white develop 5 2. Wash 1 3. Harden and stop 2 4. Wash I '10 5. Bleach silver a 2 6. Rinse. g 7. Fix 4 8. Wash 5 9. Dry (optional). 5: 10. Color develop 0 11. Wash 2 12. Harden 1 13. Wash 5 Black-and-white developer: 1-phenyl-3-pyrazolidone g Na2SO3 g 1.0 Na CO -H O g 2 .L liter-- 1 Bleach:

Sodium potassium ferricyanide g 15.0 KBr g 10.0 H2O liter 1 Color developer:

Z-aminO-S-diethylamino toluene-HCl n g 6 Na SO e N32CO3'H2O g H O liter-.. 1

In the above process a conventional acid hypo fixingsolution was used for convenience at steps 3, 7 and 12. However, this solution need not contain hypo when used at steps 3 and 12, in which case it will be apparent that no silver halide will be removed from the emulsion layer at these steps.

As shown at stage 2 of the drawing, the resultof the black-and-white development is to develop a silver image in area 12 of emulsion layer 11, and at the same time the hydroquinone derivative in'the emulsion layer is oxidized to the quinonoid form in situ with the silver image. When a hardening and fixing solution has been employed at step 3, a large part of the silver halide is removed at this point inthe process but as explained above, a silver 7 halide solvent need not be present in this solution, in which case silver halide would not be removed from the element i until step 7- hasbeen carried out.

following compositions:; 1

After bleaching and fixing the element as in steps and 7 above, the film appears substantially as shown at stage 3 of the drawing, the quinonoid image remaining in area 12 of the emulsion layer, residual unoxidized hydroquinone derivative in the remaining area of the emulsion layer-and coupler compound remaining dis =rsetl'ithroughoutthe'emulsion layer. i 1*- When color development has"been carr1ed 'ou't'according to step in the above pro,cess,,it. appe.ars..thatathe quinonoid image oxidizes the ecolorzzdeveloperin situ-and the oxidized form of the colordeveloper thus. obtained then couples with the couplercompound. in the emulsion layer to form a dye imagein wareaql 2-ias ashown in stage 4 of the drawings. vTheprocess 'asvdescribed yields a negative color reproductionflofnhe subject but, as willbe described hereinafter, may be adapted to the I production of direct color reproductions.

The coupler compound used. in the emulsion layer prepared as described above may be any of those well known in the art of color photography, such as the following:

1. 2 (2,4'di-t. amylphenoxyacetamido) 4;6-- dichloro-S-methyl phenol (Graham U.. S. Serial .No.

. 285,544, filed May 1, 1952) (blue-cyan) 2.,1 .hydroxy 2[6(2,4 di' tert. amylphenoxy) nabutyl]+naphthamide-(U. S. 2,474,293) (grey-cyan) 3. 1 (2',4',6' trichlorophenyl) -'3 [3" (2"',4"

:di tert.amylphenoxyacetarnido) benzamido] 5 pyrazolone (U. 5. 2,600,788) (blue) 1 Y N (p benzoylacetaminobenzenesulfonyl) --N.-

phenylpropyl)-p-toluidine (U. S.. 2,.298,443) (yellow) 5.1x; [oz (2,4 di tert. arnylphenoxy)acetamidolbenz oyl}:Z-methoxyacetanilide (McCrossen et al. US. Serial No. 476,159, filed December 20,4954) (y l ow) 4,4' p rnethoxybenzylidene bis {l 2,4,6 trichlorophenyl 3 [3" (2", 4'' -di tertamyl- :phenoxyacetamido) benzamido] S pyra z,olone} (bluel N C=O OCHzCONH \N/ CsHu-t A mixture of 33.6- part-s ofcoupler--3 above, -3.4 parts of anisaldehyde and 125 volumes of ethanol washeated just below the boiling point for one hour and cooled overnight. The crystallizedmixturewas. filteredandthe product collected. The crude product wa sl purified by crystallization from ethyl acetate to a meltingpoint. 915,220". 7'."1-phenyl-3-palmitoylamido-5 pyra;olone (blue).

One part of 1-phenyl 3-amino-5-pyrazolone was heated I I f ClHiP-t 2-cyanoacety1coumaroneiveulfonyl-chlorlde I swam In a 3 -l., three-necked flask, fitted with an eflicient mechanical stirrer and a thermometer, is placed 1250 cc (about 19 moles) of chlo-r'osulfonic acid. The flask is cooled in an ice-salt freezing mixture to about -10 C.,- and to the cold acid,- in small portions with vigorous stirring, is added 500 g. (2.7 moles) of the coupler 2- cyanoacetylcoumarone. Therate of addition should be such thatthe-temperature does not rise above +5 C.; about 30 mins. is required. When all the coupler has been added,-the-mixtu're is stirred at-O" for 2 hrsand thenat-room temperature overnight, or for about 15 hrs. Stirring is essential in part to prevent explosive foaming. At.the. end ofthistirne, the excess chlorosulfonio acid is decomposed bypouring the mixture with vigorous stir ring onto 10 kg. of crushed ice. The decomposition is conveniently done in a 5-gal. crock, stirring and intro ducing the mixture simultaneously from two l-l. droppingfunnels. About 10 minutes is required for the decompositiontAfter being allowed'to settle for a few minutes, the sulfonylchloride is filtered ofi onto. flannel, using two IZ-inchBiichnergfunnels. ,The two cakes are combined, vstirred with about 5 l-..of ice water, and again filtered off on allarge, funnel. The cake is again broken up,.and stirred this time-with an ice cold'solution of 500 g. of. sodium acetate in 5 l. of water. The sulfonyl chloride is finally filtered off,.washed on-the funnel with about 5 1. ,oficewater, and sucked dry. The cake, ,suc ked as free as. possible from. water, is

brokennp and dissolved in 3.1. of 300 ethyl acetate. The

ethyl acetate. solution is dried over anhydrousmagnesium sulfate and the, ethyl acetate is distilled off under redueedepressure.(40-50. mm..-Hg), the distilling flask being heated in-a water bath-which has a temperature no higher than-. vTowardthe-e'nd; of the concentration the. temperature. should '-,be as low as 20. The residue is stirred'with- 500 cc. of;benzene,-is filtered ethandwashed on the filter with about 1 l. of ether. This washing-rernoves=a small amount of tarry impurity, which tends =0 ilot-o cm to make the. product sticky, and leaves the sulfonyl chlo ride as a light yellow, powder whichappears to be quite stable, The melting point of the pure material is- 135- 136. .The yield is about 250 g. (33%). .Z-oyanGactyZcm'tma'mne 5 sulfon#N (w-pheriy'lpropy'l) p- '(t-.amyl)-anilide v A'mixture-of 78.5 g. (.265 mole) of N-y-p'henylpropyl p-t.'-axnylaniline-, 24 g; (.29 mole) of anhydrous sodium acetate,-and g. (.264 mole) of 2-cyanoacetylcoumarone-S-sulfonyl chloride (addedin the order given), in 350. cc. of glacial acetic acid, was stirred in a water bath at 50455.";v As the sulfonyl-chlon'de went into solution sodium chloride startedto precipitate. After runningfor Lhour the-reaction.mixture -setsolid due to the crystallizationof the product. The-mixture was cooled inthe ice box and fiItered.- 'After being sucked as dry as possible, the residue was washed on the filter with cc. of :methyl alcohol. The product was thenslurried with cc. of methyl alcohol, filtered, and rinsed with 50 cc, of methyl alcohol. This washing process was repeated using200 cc. .of ethyl. ether. and the residue, rinsed with 200 cc. of e'ther'till the filtrate was any faintly colo red.

After 'be'ing sucke d drytlie product was meat nn same manner with Watf'GOD O C- ili 811). It was thh 'of methyl p,n-amoxybenzoate.

air-dried'slur'riecl with 150 cc. of-ether, filtered-and dried. Yield of cream-colored product, 72 g. (51.5%). M. P. 137-139.

9. Di-B-naphthoylmethane (blue-grey) COCHzCO 'melting at 168l69.

10. p-n-Amoxybenzoyl-fl-naphthoylmethane (green-grey) -o o orno 000 051111 In a 500-cc. three-necked flesk are placed 17 g. (0.1 mole) of methyl fl-naphthy'l ketone and 90 g. (0.4 mole) The flask is fitted with an eccentric type stirrer and a still-head. head is connected through a water cooled condenser to a 500-cc. suction flask for removal of methanol during the reaction. The reaction flask is heated in an oil bath maintained at l65175, vigorous stirring is begun, and sodium methoxide is added in small increments. The reaction mixture turns dark immediately and methanol begins to distill. The additions which take about fifteen minutes are made as rapidly as evolution of methanol permits. The reaction mixture gradually thickens, and in about thirty minutes evolution of methanol ceases and the product sets to a solid mass. After heating fifteen minutes longer, the oil bath is removed and the flask chilled in running water.

The reaction mixture is stirred alternately with IOO-cc. portions of water and benzene. This'requires about 400 cc. of each to obtain solution of the Whole mass. Ice is added to the emulsion which is then made acid to Congo red with dilute sulfuric acid. The benzene layer is next Washed with three ZOO-cc. portions of 5% sodium bicarbonate, and with two ZOO-cc. portions of 5% sodium carbonate. The benzene layer is next washed with 200 cc. of 5% sodium hydroxide, and then shaken thoroughly with dilute sulfuric acid until the benzene layer is no longerv cloudy. After another wash with dilute sodium bicarbonate, it is washed thoroughly with cold water until neutral. The benzene layer is then dried over calcium chloride, and concentrated in vacuo. The excess methyl p-n-amoxybenzoate is removed by careful distillation at low pressure. The recovered ester,

amounts to 45 g.

The residue is dissolved in 750 cc. of ethyl alcohol and treated with l g. of decolorizing charcoal. The solution is filtered hot through a steam heated fluted filter. The yield of product melting at 93-95" is 19.5 g. This is again crystallized from 500 cc. of alcohol giving 16 g. (44%) of light yellow flakes, M. P. 9697.

l1. 1,3-diethylthiobarbituric acid (blue-grey) (J. A. C. S.

In the above tabulation of coupler compounds, following the name of each of the compounds'is given the approximate color of the dye image obtained when the given coupler is employed in the above process with the given color developing agent and given hydroquinone derivative in the emulsion layer.

The still ample, in the Jelley and Vittum U.

critical in that the developingagent should not nophenol,

It has been ascertained that when the firstcoupler compound of the above tabulation is used in the process, most of the dye in the resulting image is identical to that obtained in conventional color development processes in which color development takes place in the presence of the coupler and exposed silver halide. On the other hand, the dye image obtained when coupler No. 4 is used is a mixture of two yellow dyes in approximately equal amounts, it appearing that the quinonoid image obtained in this case during the black-and-white development step functions not only as an oxidizing agent for the color developing agent but also enters directly into the dyeforming reaction.

Dye image formation in the described process was most rapid and extensive when coupler compounds Nos. 1, 3, 4, 5 and 7 employed in the emulsion layer together with the mentioned hydroquinone derivative. These couplers are therefore preferred for use in my process.

Other hydroquinone derivatives which may be used in the emulsion layer prepared as described above include n-octadecylhydroquinone and 2-hexadecyl-6-methylhydro- -quinone. Dialkylhydroquinones, where both alkyl groups are larger than methyl, as, for example, 2,5-dioctylhydroquinone, do not give dye images in this process. 7

The coupler solvent such as di butyl phthalate employed for dispersing the hydroquinone derivative and coupler in the emulsion layer is not especially critical and can be selected from the substantially water-insoluble, lowmolecular weight organic crystalloidal materials having a boiling point above about C. disclosed, for ex- S. Patent 2,322,027 and other coupler solvents known in the art.

The developing agent used in the black-and-white developing solution of step 1 of the above process is fairly be a color developing agent such as a paraphenylenediamine compound but should have a high development activity and should be capable in the black-and-white development step of the process of leading to the oxidation of the hydroquinone derivative in the emulsion layer to the quinonoid form. The p-aminophenols and N-alkyl oaminophenols, such as p-aminophenol, 2-methyl-4-ami- 2-methyl-4-diethylaminophenol, N-methyl-paminophenol, and o-methylaminophenol are very useful as Well as the 3-pyrazolidone silver halide developing agents, a number of which are disclosed in the James et al. U. S. Patent 2,688,549, granted September 7, 1954. In addition to l-phenyl-3-pyrazolidone, 1-phenyl-4-methyl- 3 pyrazolidone, 1 phenyl 4,4-dimethyl-3-pyrazolidone, and l-p-tolyl-4,4-dimethyl-3-pyrazolidone are particularly useful. 4-phenylcatechol was useful, and catechol was moderately etfective. Hydroquinone and o-aminophenol were not useful in the process.

The color developing agents used in step 10 of the process are not especially critical and can be selected, for example, from the p-phenylenediamines known in the art, and can be expected to yield dye images of somewhat different color with a particular coupler compound.

My process can be adapted to the production of multicolor images by the incorporation of different coupler compounds in the emulsion layers of a multilayer film whose emulsions are sensitive to different regions of the spectrum. In this case the same hydroquinone derivative or different hydroquinone derivative selected from those mentioned above as useful in the process, can be incor porated into the respective emulsion layers together with the given coupler compounds. A suitable film can have the usual red, green and blue-sensitive emulsion layers superimposed with a yellow filter between the green and blue-sensitive emulsion layers. In the emulsion layers are incorporated coupler compounds such as those mentioned yielding subtractively colored dye images in the process. In case developing-out emulsions have been used in the emulsion layers, such multilayer elements are adapted to the production of original color negatives, or

' olor negative transparenciesmay lieprinted there'on and :c'olor positives obtained by proeessiiig the film asde- Direct-positive"eo1or -iepioductidhs of a siibject'can be 'reajdily ob'tained using my proc'ess' hy-employing in the sensitive elements -a'- direct positive isilver halide emulsion such as V the known =iriter l iatent image emulsions, in which case for the blaek-and-Whi'te' develoiin'e'nt 'step 'of my 'process 'a developer =m'aybe used containing a suitable quamity -'of "a hydraiine foggingegent; Emul- "sions and developers si1itabIe ior this purpose are described in the Haist et alaU': SfiPat'nt 2,'685-,5-14,granted August 3, 1954. In the hydrazine-containing developers described in that patent; eorrespending 1 to the black and =vvhite developer of step l of my process described above, the p-aminophenol ;and 3{pyr'a z olidone'developing agents developing agents may -heu'sd in "combination, or example, the combination 6f'N methybp arninophen'olsulfate together with l phenylffipyraielidone.

"The process" of my invention isapplieable to the production'of colored image'sginothen l iinds 'of emulsion layers sueh' asmiXe'd packet types of; emulsion l'ay e'rs, "in which easethe hydroquinone derivative is incorporated along with the couplers in the iackets.

Whatl-claim-is;

19A photogra 'ahic reproduction process which comprisesexposing to asubieet-a silver halide emulsion layer containing a- T mixture 'of *a coupler *compound reactive with the oxidation product ofa'ptimary aromatic amino silverhalide developing "agent tdform a dye'and a hydroquinone derivativebf the elass'consisting'of n-o'ctadecylhydroqiiinon'e, sec.-octadecylhydroquinone and Z-h'exa- '-decyl-G-mthylhydroquinone dispersed in the emulsion layer by means of a suh antially water-insoluble, low

molecular weight, -ot'g'anic cry s'talldidalmaterial having a boiling point above about-1'75 Ci, =developin'g the exposed emulsion layer with an alkaline solutiori'ofadeveloping agent of the elass consistingof p-aminophenol, N-alkyl-o-aminophenol, and 3-pyrazolidone silver halide developing agents therebyjforming"in -theemulsion layer an image of silver and oxidized hydroquinone derivative, removing the silver image and residual silver halide from the emulsion layer, treating the remaining oxidized hydro- 'quinone derivative-imagednthe presence of the; -coupler compound with an;alkaline-solution of :1 pqzvhenylenediamine silver-halide?developing agent to forma dye image inthe? region of original; silver-image.

1 *2, The process; of claim '1 inzyvhich the coupler compound I is 242 ,4f-di tt-amylphenoxyacetamido1)-4,6-dibenzoy1}'-2-methoxyaeetanilide.

Ref'efences'Cited in the 'file'fof 'this patent UNITED-STATESPATENTS 2206326 jSjchin l uly ,2, ,1940 2,249,541 iSc'hinzel July 15,1941 2,728,659 Lo'riweflal Dec.' 27, 1955 

1. A PHOTOGRAPHIC REPRODUCTION PROCESS WHICH COMPRISES EXPOSING TO A SUBJECT A SILVER HALIDE EMULSION LAYER CONTAINING A MIXTURE OF A COUPLER COMPOUND REACTIVE WITH THE OXIDATION PRODUCT OF A PRIMARY AROMATIC AMINO SILVER HALIDE DEVELOPING AGENT TO FORM A DYE AND A HYDROQUINONE DERIVATIVE OF THE CLASS CONSISTING OF N-OCTADECYLHYDROQUINONE, SEC.-OCTADECYLHYDROQUINONE AND 2-HEXADECYL-6-METHYLHYDROQUINONE DISPERSED IN THE EMULSION LAYER BY MEANS OF A SUBSTANTIALLY WATER-INSOLUBLE, LOW MOLECULAR WEIGHT, ORGANIC CRYSTALLOIDAL MATERIAL HAVING A BOILING POINT ABOVE ABOUT 175*C., DEVELOPING THE EXPOSED EMULSION LAYER WITH AN ALKALINE SOLUTION OF A DEVELOPING AGENT OF THE CLASS CONSISTING OF P-AMINOPHENOL, N-ALKYL-O-AMINOPHENOL, AND 3-PYRAZOLIDONE SILVER HALIDE DEVELOPING AGENTS THEREBY FORMING IN THE EMULSION LAYER AN IMAGE OF SILVER AND OXIDIZED HYDROQUINONE DERIVATIVE, REMOVING THE SILVER IMAGE AND RESIDUAL SILVER HALIDE FROM THE EMULSION LAYER, TREATING THE REMAINING OXIDIZED HYDROUNINONE DERIVATIVE IMAGE IN THE PRESENCE OF THE COUPLER COMPOUND WITH AN ALKALINE SOLUTION OF A P-PHENYLENEDIAMINE SILVER HALIDE DEVELOPING AGENT TO FORM A DYE IMAGE IN THE REGION OF ORIGINAL SILVER IMAGE. 